Hydrogen process



Patented Sept. 2, 1952 Coiey; Valparaiso, Ind., assignorsto. Standard Oil-Company, Chicago, 111-.,` a corporation of Indiana y, Application, neeembefsi, 1949; seria1N0-1`ss2s2* 1 This invention relates toa process of making hydrogen and more particularly it relates, tofV a process of makingA substantially pure hydrogen from carbon monoxide or from Water' gas. The invention is illustratedby a drawing whichshows diagrammatical-ly an apparatus for carrying outr the process. v

In the manufacturev of hydrogen, it hasl long been a diiiicult problem to produce substantially pure. hydrogen on a commercialscale. Many hydrogenation. processes, .such as hydrogenation. of oils and fats, require hydrogen .which isA relatively free from contamination with other gases. Carbon monoxideis especially detrimental to certain catalytic hydrogenation processes where it. Ace

exerts a poisoning .eiect on the catalyst. cordingly, for manysuchprocesses. it has been the practice to use electrolytic hydrogen obtained.

from the. electrolysis. of water atconsiderable `exe pense. for electric. power.v l.

In the manufacture.y of hydrogen from carbon monoxide or water gas, ithasheretofore been the practice. to conduct the water gas in admix-- ture with steam over av fshift catalyst,y the followingreaction, occurring.:

This reaction is moderately exothermicz and. ac-- cordingly it is necessary to providev some. degree. of cooling. The reaction temperatureu ordinarilyl employedisabout 750 toz850 F;

Whenv equimolar amounts of CO and H2O' ar employed at' a temperature; of 800- the reaction proceeds only partiallyiingthe desired direc;- tion so that, at equilibrium, onlyv 'I5 per cent of' COihas been, converted; to CO2, with the: result` thatv much unconverted CO remains' with the hydrogen product.v Ordinarily it is` the practice.

to increase greatly the amountzof Water or steam employed in` order to shift the. equilibrium further` in the desired' direction, and it is. not uncommon to employ ten. volumes; of' steam. per

Volume of CO- in` the reaction mixture, this amount corresponding to about ten timesthat theoretically required; Thiszvsubstantially in-V creases the cost of the-operation, not only because; of' the increased steamjrequirement" but because of the increased size of rtheapparatus required for handlingthe larger volumes ofrgas; increase in cooling'fwater'requirements, etc.-:.i

One object of our 'process is to .reduce the? amount of steam; employedv in the shift conversion of CO to hydrogen and CO2. *Another` object. oi ourfprocess isto produce a substantiallypure grade ofv hydrogen freey of CO3' Still ans claims. (el. 23g-2,14)

other objectof our process is to eliminate xp'en`-r sive;l purification steps including CO2 absorption by .aqueous solutions.l Thek lprocess willi-be more fully understood by referring to vthe drawingv in which A isa Water gas; generator-B- isV afco'ntinuous adsorption towerjand "C is af shift converter. Y

.Water gas for our process can be supplied fromY various sources such as'Y the usrialwater-gasigen erator ini which a bed of' coke isalternately blasted' with air and steam. -Water gas can also be'- preparedY from coke by the action vof oxygen and' steam at water gas` reaction temperatures,v e. g; 1`800to2400 F; This operation can be'conduct'ed" in theA wellknoWn"Winkler Iiuidized: bed genenator or the powdered coke, oxygen and steam canJbe interacted ina suitable insulated reaction chamber to. produce a mixture 'of CO andv hydrogen continuously. v

. The. drawing describes a water gas generator Instead et methane lwemay alsovuse other gas-A eous fuelsy such vas'ethalne, propane 'and butane.

Itis usually desirable to operate, tljiew'ater gas generator 'under substantial pressure,V e. g, '50' to 600i p. sf. i., a'suitable pressure being*about'300`V p. S. 1. significantly with their water gas .reaction and when:handlingA large .volumes of gasesthe' use of pressure has-the advantage .offreducingthe' size of the. equipment Aforagiven volume of'gasv thrupllt. If desired, the..` pressure-maybe in. creasedl by compression before, the, gasis `chargedwadScptQn .tower'Bl Y, The hot'gas'ebus'reaction products pass from, generator A by line I4 Ato yheat exchanger. [5, in whichv part 'of the IheatI of the lgases is usefully absorbed; for examplef,f` by 4heating the gases charged tothe generator A. 'IYhusitI is desirable' Pressures ofV this'order vdo not interfereto preheat the oxygen to about 800 to 1200" F., and where methane is employed as a fuel this can be preheated to 1200" to 1400* F. From exchanger I5, gases are passed thru cooler i6 thence into Water separator where any excess water is collected and discharged by line I8. The gases can' be additionally dried, e. g. with silica gel, calcium chloride, etc., if desired. The gases then pass by line I9 to adsorption tower B where they are brought into contact at a temperature in the range of about 'I5-250 F. With a downwardly flowing stream or moving bed of adsorptive charcoal or other suitable adsorbent. In some cases bauxite or silica gelcan be used for the purpose, and mixtures of these and other adsorbents can be employed.

The adsorbent flowing downward in tower-B adsorbs from the gases, Water vapor, CO2, and

for this purpose. temperature, the supply of oxygen is cut off.

The temperature of the shift converter C may also -be controlled by means of a cooling fluid surrounding the catalyst tubes therein, circula- -tion'of the cooling fluid being eifected to hold the temperature at any desired point. Following-are typical shift catalysts for use in the reac- CO; the hydrogen, which is adsorbed to only a small extent, flows up through the cooling section 52 and through the heating section 5| countercurrent to the downward .flowing carbon, and is withdrawn from the tower by line leading to cooler 20a and separator 20h.

Theadsorbent charcoalcarrying CO, CO2' and H2O passes downward thru the tower and is heated at or near the bottom by heating coil 2|. The temperature in the cooling section-52 at the upper partof the tower B is kept relatively low, e. g. 50 to 125 F., by the use of cooling coils such as those shown at 22. Instead of supplying heat -to the charcoal by heating coil 2| located Within the tower, the adsorbent may be withdrawn and heated externally in a suitable heat exchanger from which the desorbed gases are withdrawn and returned to the tower. It is desirable to heat the adsorbent to a temperature suilicient to desorb substantially all the adsorbed gases, particularly any residual CO. A suitable temperature is about 500 to r100" F. Desorption of the gases from the charcoal is also greatly facilitated by the introduction of steam by line 23 and superheated steam may be used for this purpose to increase the heat input at the bottom of the adsorber. 1 '4 The desorbed gases owing upward thru the Y tower countercurrent to the downflowingstream of charcoal establish a temperature gradient from the bottom to the midpoint ofthe tower where the feed vgas is introduced. If desired, additional heating coils can he interspersed inv stream of CO by line 25and the mixture then' passes by line 21 to converter C. In case rela# tively pure CO is available as a feed gas it can be' charged directly to the shiftconverter instead of to the adsorption tower. Here the CO in contact'with theY shiftl catalyst is converted to CO2 and an equivalent amount ofV hydrogen is produced. n Hydrogen -and unconverted CO together with the CO2 pass from-therconverterby line 28 thru cooler 25 thence by line 30;to the adsorption tower B. Temperature in the'shift converter can bevcontrolled by'recycling hot-gasesv tion tubes of converter C FezOa 74.2 89.8 Cr203 Y 10.0 7.5 MgO 0.2

H2O (combined) 14.0- 1.3 Inerts 1.6 1.4

Returning to the operation of the adsorption tower B, the charcoal ilowing thru zone 31 yis substantially entirely freed of CO. It then passes into z onel 38 where, at temperatures of about 190 to 400 substantially all CO2 is eliminatedv along'with steam. The CO2 is Withdrawn by line 39 and Adischarged from the system. The denuded charcoal, which is essentially in equilibrium with pure steam at the temperature and` total pressure of the bottom of the column, passes from the bottom of the tower by line 40 and is thence elevated by line 4| to a point above the top of the tower for recycling therein. Mechanical elevators may be used for this purpose, however the drawing shows the use of a gas lift instead. Hot gas is circulated from the top of separator 43 via line 42 and blower 48 to pick up rcharcoal from standpipe 40, iluidizing it and conducting it tothe :cyclone separator 43 from which the charcoal is returned to the adsorption tower by line 45. The hot charcoal flowing from the top of the column down thru the heated section 5| is stripped of adsorbed steam by the countercurrently rising stream of hydrogen', so that when the charcoal has subsequently passed thruthe cooling section 52 it will have full adsorption capacity for CO. The heat required for stripping the steam from the'charcoal in' 5| is suppliedbyV heating coil 50, which can be con-` trolled to hold thetemperatur'e of the charcoal" at about 400 to 700 F. and supply the latent heat needed to desorb water from the adsorbent." The charcoal shouldbe provided in the form of pellets or granules of sufficient dimensions to permit free flowing of gases therethru. Granules ranging. in size all the way from one-fourth inch in diameter to50'to 1'00 mesh can be employed? and 10 to 30 meshisa satisfactory size range.

`If the adsorption tower is operated in suchl a` manner as to allow some residual CO2 tol remain on the charcoal, some contamination oflhydrogen with CO2 withdrawn by line 20 will result. If operated in this manner it will usually 'be' necessary Yto provide a scrubbing tower for removal-of the small amount of contaminating- CO2, e; g'. l to 5 volume percent, entering the hydrogen in this way. lThe removal 'of small amounts of'contaminating CO2 by alkali washing, etc.,.is not a serious problem when' compared with the problem of removing large volumes of CO2 inthe usual CO conversion process.

cordingly, where pure hydrogen substantially free of nitrogen is desired, it is important to employ feed gas which is nitrogen free. Where the fuel supplied to the water gas generator `A is natural gas, considerable nitrogen contamination is usually present. If propane is used as the fuel, it is relatively easy to obtain a nitrogen free water gas providing the oxygen supplied by line l is relatively nitrogen free. y

In general, the water gas from generator A will contain one or two percent unconverted methane. This hydrocarbon is readily adsorbed on the charycoal is adsorption tower B and does not contaminate the hydrogen product. However, in the desorbing zone 37 it is eliminated with the CO and passes by line 2li to the shift converter and thence back to the adsorption tower by line where it is readsorbed. Accordingly, even though only a small amount may be present in the water gas,

methane tends to build up in the system requiring an occasional purge, for example thru vent 46. Alternatively, a portion of the gas from the tower where the hydrocarbon concentration is greatest can be continuously or intermittently recycled by line 47 to the water gas' generator,

where it is introduced with the fuel by line Il. Our process provides great flexibility in the manufacture of commercial hydrogen. Tne efficiency of the shift reaction is greatly increased by employing only slightly more than the theoretical amount of steam required for CO conversion. Thus, by employing only 1.0 mol of steam per mol of CO, approximately 75 percent of the CO is converted to CO2. We prefer to operate the converter C with a mol ratio of steam -to CO within the range of about 1:1 to 2: 1. The resulting gas mixture usually contains a lower proportion of hydrogen than. that in the feed gas supplied by line I9. Accordingly, it is usually desirable to introduce the products from the shift converter at a lower point in the adsorption tower B, where the hydrogen concentration in the tower is substantially the same as the hydrogen concentration in the gas from the shift converter. Various modications of our process will be apparent to those skilled in the art.

Having thus described our process, we claim: 1. The method of producing CO-free H2 from a gas mixture containing substantial amounts of Hz, CO, CO2 and H2O, which method comprises introducing said mixture at an intermediate level of an adsorption zone into a downwardly flowing column of a granular solid adsorbent capable of adsorbing CO, CO2 and H2O, passing said introduced gases upwardly counter-current to the downwardly flowing adsorbent under conditions for adsorbing substantially al1 CO and CO2 from the H2 in a countercurrent portion of the adsorption zone, removing unadsorbed Hz from the upper part of said adsorption zone, selectively desorbing CO from the downwardly flowing adsorbent at a level substantially below the level at which the gas mixture is introduced, adding to the desorbed CO an amount of H2O which is at least 1 mol of H2O per mol of CO, but not substantially more than about 2 mols of H2O per mol of CO, contacting said (JO-H2O mixture at a conversion temperature not higher than about 850 F. with a shift catalyst to convert most, but not all, of the CO-I-IzO to CO2-H2, cooling the effluent from the contacting step and returning the cooled effluent to a level in the adsorption zone which is above the CO-desorption level and below the countercurrent portion of the adsorption zone whereby H2 produced in the contacting step passes upwardly in the adsorption zone and is removed with the initially introduced hydrogen component and unreacted CO from the contacting step passes downwardly for desorption and further contacting with H2O in the presence of the shift catalyst so that CO is thus recycled to extinction, passing adsorbent containing initially introduced CO2 and CO2 from the contacting step downwardly to a CO2 desorption zone and removing CO2 from the adsorbent in said CO2 desorption zone, heating the catalyst to remove substantially all adsorbed components therefrom whereby the adsorbent isdenuded and returning said denuded adsorbent to the upper part of said adsorption zone for repeating its cycle.

2. rlhe method ofclaim 1 which includes the step of conveying solids from the bottom of the adsorption zone to the top of the adsorption zone bythe gas lift action of compressed hydrogen withdrawn from the top of the adsorption Zone.

3. The method of lclaim 1 wherein the adsorbent is charcoal.

4. The method of claim 1 wherein the shift catalystpconsists essentially of FezOs and CrgOa with the former present in predominating amounts.

5. The method of claim 1 which includes the step of introducing steam in the CO2 desorption zone for insuring the removal of all CO2 from the adsorbent, introducing adsorbent containing adsorbed steam at the top of the adsorption zone. heating said adsorbent at the top of said zone to a temperature in the range of 400 to 700 F., stripping the hot adsorbent with unadsorbed hydrogen for eliminating adsorbed steam from the adsorbent and cooling the adsorbent as said adsorbent enters the top of the countercurrent portion of the adsorption zone. Y

6. The method `of claim 5 which includes the step of cooling the eiiiuent hydrogen stream from the top of the adsorption zone to eiect condensation of' steam and separating condensate from uncondensed hydrogen.

LEONARD W. RUSSUM. JOSEPH F. COFFEY.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,422,007 Soddy July 4, 1922 1,595,683 Burrell et a1 Aug. 10, 1926 1,742,247 Godel Jan. 7, 1930 1,825,707 Wagner Oct. 6, 1931 2,070,099 Twomey Feb. 9, 1937 2,254,799 Erdmann Sept. 2, 1941 2,495,842 Gilliland Jan. 31, 1950 2,519,342 Berg Aug. 22, 1950 OTHER' REFERENCES Handbook of Physics and Chemistry, 28th-ed. (pages 364-365, 388-391), by C. D. Hodgman, published by Chem. Rubber Pub. Co., Cleveland. Ohio.

Text-Book of Physical Chemistry, by Glasstone, pag-es 1173, 1175 (sixth ed), D. Van Nostra-nd Co., Inc., N. Y., publishers. 

1. THE METHOD OF PRODUCING CO-FREE H2 FROM A GAS MIXTURE CONTAINING SUBSTANTIAL AMOUNTS OF H2, CO, CO2 AND H2O, WHICH METHOD COMPRISES INTRODUCING SAID MIXTURE AT AN INTERMEDIATE LEVEL OF AN ADSORPTION ZONE INTO A DOWNWARDLY FLOWING COLUMN OF A GRANULAR SOLID ADSORBENT CAPABLE OF ADSORBING CO, CO2 AND H2O, PASSING SAID INTRODUCED GASES UPWARDLY COUNTER-CURRENT TO THE DOWNWARDLY FLOWING ADSORBENT UNDER CONDITIONS FOR ADSORBING SUBSTANTIALLY ALL CO AND CO2 FROM THE H2 IN A COUNTERCURRENT PORTION OF THE ADSORPTION ZONE, REMOVING UNADSORBED H2 FROM THE UPPER PART OF SAID ADSORPTION ZONE, SELECTIVELY DESORBING CO FROM THE DOWNWARDLY FLOWING ADSORBENT AT A LEVEL SUBSTANTIALLY BELOW THE LEVEL AT WHICH THE GAS MIXTURE IS INTRODUCED, ADDING TO THE DESORBED CO AN AMOUNT OF H2O WHICH IS AT LEAST 1 MOL OF H2O PER MOL OF CO, BUT NOT SUBSTANTIALLY MORE THAN ABOUT 2 MOLS OF H2O PER MOL OF CO, CONTACTING SAID CO-H2O MIXTURE AT A CONVERSION TEMPERATURE NOT HIGHER THAN ABOUT 850* F. WITH A SHIFT CATALYST TO CONVERT MOST, BUT NOT ALL, OF THE CO-H2O TO CO2-H2, COOLING THE EFFUENT FROM THE CONTACTING STEP AND RETURNING THE COOLED EFFLUENT TO A LEVEL IN THE ADSORPTION ZONE WHICH IS ABOVE THE CO-DESORPTION LEVEL AND BELOW THE COUNTERCURRENT PORTION OF THE ADSORPTION ZONE WHEREBY H2 PRODUCED IN THE CONTACTING STEP PASSES UPWARDLY IN THE ADSCRPTION ZONE AND IS REMOVED WITH THE INITIALLY INTRODUCED HYDROGEN COMPONENT AND UNREACTED CO FROM THE CONTACTING STEP PASSES DOWNWARDLY FOR DESORPTION AND FURTHER CONTACTING WITH H2O IN THE PRESENCE OF THE SHIFT CATALYST SO THAT CO IS THUS RECYCLED TO EXTINCTION, PASSING ADSORBENT CONTAINING INITIALLY INTRODUCED CO2 AND CO2 FROM THE CONTACTING STEP DOWNWARDLY TO A CO2 DESORPTION ZONE AND REMOVING CO2 FROM THE ADSORBENT IN SAID CO2 DESORPTION ZONE, HEATING THE CATALYST TO REMOVE SUBSTANTIALLY ALL ADSORBED IS DENUDED AND RETURNING WHEREBY THE ADSORBENT IS DENUDED AND RETURNING SAID DENUDED ADSORBENT TO THE UPPER PART OF SAID ADSORPTION ZONE FOR REPEATING ITS CYCLE. 